EP0275324B1 - Aromatische polyester mit guter wärmebeständigkeit - Google Patents

Aromatische polyester mit guter wärmebeständigkeit Download PDF

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EP0275324B1
EP0275324B1 EP87904936A EP87904936A EP0275324B1 EP 0275324 B1 EP0275324 B1 EP 0275324B1 EP 87904936 A EP87904936 A EP 87904936A EP 87904936 A EP87904936 A EP 87904936A EP 0275324 B1 EP0275324 B1 EP 0275324B1
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Prior art keywords
structural units
vii
mole
viii
total
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EP0275324A1 (de
EP0275324A4 (de
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Masaru Okamoto
Toshihide Inoue
Shiro Kataoka
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Toray Industries Inc
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Toray Industries Inc
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Priority claimed from JP61175742A external-priority patent/JP2525370B2/ja
Priority claimed from JP61183374A external-priority patent/JPH0798859B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings

Definitions

  • polyester prepared by copolymerizing phenylhydroquinone, terephthalic acid and/or 2,6-naphthalenedicarboxylic acid with p-hydroxybenzoic acid Japanese Patent Publication No. 500,215/1980
  • a polyester prepared by copolymerizing 2,6-dihydroxynaphthalene and terephthalic acid with p-hydroxybenzoic acid Japanese Patent Laid-Open No. 50594/1979
  • a polyester prepared by copolymerizing 2,7-dihydroxynaphthalene, isophthalic acid and/or terephthalic acid with p-hydroxybenzoic acid Japanese Patent Laid-Open No.
  • the present inventors have carried out polymerisation, molding and evaluation of various new polyesters with a view to obtaining polyesters capable of giving moldings having good flow characteristics, heat resistance and mechanical properties and have found that aromatic polyesters consisting of specified amounts of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone and terephthalic acid or terephthalic acid and isophthalic acid (with or without copolymerisation of dihydroxy compounds such as t-butylhydroquinone and so on) could satisfy the above described purpose.
  • an aromatic polyester having good heat resistance comprising the below described structural units (i), (v), (vi) and (vii) with or without the structural unit (viii), where the molar ratio of the structural unit (i) to the total of the structural units [ (i) + (vi) + (vii) + (viii) ] is from 60 to 90%, the molar ratio of the structural units [ (vi) + (vii) + (viii) ] to the total of the structural units [ (i) + (vi) + (vii) + (viii) ] is from 10 to 40%, the molar ratio of the structural unit (vi) to the total of the structural units [(vi) + (vii)] is 50 to 95%, the molar ratio of the structural unit (vii) to the total of the structural units [(vii) + (viii)] is 5 to 100% and the molar ratio of the total of the structural units [ (vi) + (vii) + (viii) ] to the structural unit (v) is 1; and
  • the polyester is comprised of only the structural units (i) to (iii) in the present invention, it is preferable that 65 to 85 mole % of the carbonyl groups in (ii) and (iii) are in para position.
  • the above described structural unit (i) represents the structural unit of polyester prepared from p-hydroxybenzoic acid.
  • the above described structural unit (ii) represents the structural unit of polyester prepared from 4,4'-dihydroxybiphenyl and terephthalic acid or terephthalic acid and isophthalic acid.
  • the above described structural unit (iii) represents the structural unit of polyester prepared from hydroquinone and terephthalic acid or terephthalic acid and isophthalic acid.
  • the above described structural unit (iv) represents the structural unit of polyester prepared from one of the dioxy compounds selected from t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, chlorohydroquinone and methylhydroquinone and terephthalic acid or terephthalic acid and isophthalic acid.
  • the molar ratio of the structural unit (i) to the total of the structural units [ (ii) + (iii) + (iv) ] is 60 to 90 mole %, preferably 65 to 80 mole %. If the said ratio is more than 90 mole % or less than 60 mole %, this is not desirable as the flow characteristics and heat resistance become poor.
  • the molar ratio of the structural unit (ii) to the total of the structural units [(ii) + (iii)] is 50 to 95 mole %. If the said ratio is less than 50 mole %, the heat resistance is poor and, if more than 95 mole %, the flow characteristics become poor. These are therefore not desirable.
  • the molar ratio of the structural unit (iii) to the total of the structural units [(iii) + (iv)] is 5 to 100 mole %. If the said ratio is less than 5 mole %, this is not desirable as either the flow characteristics, the heat resistance or the mechanical properties are poor.
  • the carbonyl groups in the structural units (ii) and (iii) have a relation of para or meta position to each other and more than 65 mole % thereof are in para position. If the value is less than 65 mole %, it is not desirable as the heat resistance is not sufficient.
  • the polyester is comprised of only the structural units (i) to (iii), 65 to 85, preferably 65 to 80, mole % of the carbonyl groups of the structural units (II) and (III) may be in para position to each other, and more preferably 72 to 77.5 mole %. If more than 80 mole% are in para position, this is not desirable as the flow characteristics become poor.
  • the polyester is comprised of the structural units (i) to (iv)
  • the molar ratio of the structural unit (iv) to the total of the structural units [(iii) + (iv)] is 10 to 80 mole %
  • t-butylhydroquinone, phenylhydroquinone and 2,6-dihydroxnaphthalene are preferable among dihydroxy compounds constituting the structural unit (iv).
  • Aromatic polyesters of the present invention can be prepared by applying the conventional polycondensation methods for polyesters and no special limitation exists in the method of preparation.
  • the following methods (1) to (4) can be listed as the representative methods.
  • melt viscosity of aromatic polyesters of the present invention 50 to 15,000 poises are preferable and 100 to 10,000 poises are more preferable.
  • melt viscosity are measured by means of Kota type flaw tester at the temperature of liquid crystal starting temperature plus 30 to 50°C under a shear rate of 1,000 to 3,000 sec ⁇ 1.
  • the logarithmic viscosity of these aromatic polyesters dissolved at a concentration of 0.1 weight % in pentafluorophenol at 60°C is 1.0 to 20.0 dl/g, and 2.0 to 10.0 dl/g is especially preferable.
  • Aromatic polyesters of the present invention thus prepared have melting points lower than 400°C and conventional melt moldings such as extrusion molding, injection molding, compression molding, blow molding and so on can be therefore applied to prepare fibers, films, three dimensional moldings, containers and hoses and so on.
  • aromatic polyesters of the present invention when molding is carried out, required characteristics can be given to aromatic polyesters of the present invention by adding reinforcing materials such as glass fibers, carbon fibers, asbestos, additives such as fillers, nucleation agents, pigments, anti-oxidative agents, stabilizers, plasticizers, lubricants, releasing agents and flame retardants and other thermoplastic resins.
  • reinforcing materials such as glass fibers, carbon fibers, asbestos, additives such as fillers, nucleation agents, pigments, anti-oxidative agents, stabilizers, plasticizers, lubricants, releasing agents and flame retardants and other thermoplastic resins.
  • the strength of the moldings obtained can be improved by heat-treatment and their modulus can be improved as well in most cases.
  • This heat-treatment can be carried out by heat-treating the moldings in either an inert atmosphere (for example, nitrogen, argon, helium or steam), an oxygen-containing atmosphere (for example, air) or under reduced pressure at a temperature below the melting point of the polymer.
  • This heat-treatment can be done either in the stretched state or in the unstretched state for scores of minutes to several days.
  • the moldings prepared from new aromatic polyesters of the present invention have good optical anisotropy and flow characteristics due to the parallel molecular arrangement and excellent mechanical properties and heat resistance as well.
  • reaction was carried out under nitrogen atmosphere at 250 to 360°C for 3 hours and the pressure was thereafter reduced to 1 mmHg.
  • Polycondensation reaction was completed by heating for more than one hour to give approximately the theoretical amount of acetic acid distillate and to obtain a brown polymer.
  • Five batches of the polymerization were carried out under the same conditions and the polymers recovered were ground, using a grinding machine manufactured by Horai Co., Ltd.
  • This polyester was placed on the sample plate of a polarization microscope and the optical anisotropy was observed by elevating temperature. Good optical anisotropy was thereby observed above 305°C.
  • the melt viscosity of this polymer was 6,500 poises at 350°C under the rate of shear of 1,000 sec ⁇ 1, thus showing very good flow characteristics.
  • Test pieces of 1/8" in thickness x 1/2" in width x 5" in length and test pieces for the mold-notch impact strength determination of 1/8" in thickness x 2 ⁇ 1/2" in length of this polymer were prepared by using Sumitomo-Nestal injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Machine Industries Co., Ltd.) under such conditions that the cylinder temperature and the mold temperature were 350° and 30°C respectively.
  • the value of Izod impact strength (mold-notch) was 34 kg ⁇ cm/cm, which is high.
  • Heat distortion temperature of the test piece of 1/8" in thickness measured by using the heat distortion measuring apparatus manufactured by Toyo Seiki Co., Ltd. was 264°C (18.56 kg/cm2), thus showing excellent heat resistance.
  • p-Acetoxybenzoic acid (i), 4,4'-diacetoxybiphenyl (vi), hydroquinone diacetate (vii), terephthalic acid (v1) and isophthalic acid (v2) were introduced into polymerization test tubes and the polycondensation reactions were carried out under the same reaction conditions as those of example 1 to obtain polymers.
  • Homogeneous melt polymerization was possible in examples 2 to 6, but in the case of comparison examples 1 and 7, the polymers adhered to the stirrer and were partly solidified during polymerization, thus making homogeneous melt polymerization impossible.
  • reaction was carried out under nitrogen atmosphere at 250 to 340°C for 3 hours and the pressure was thereafter reduced to 1 mmHg after the temperature was elevated at 350°C.
  • Polycondensation reaction was furthermore carried out by heating for more one hour to obtain a brown polymer.
  • Five batches of the polymerization were furthermore carried out under the same conditions and the polymers recovered were ground using a grinding machine manufactured by Horai Co., Ltd.
  • This polyester was placed on the sample plate of a polarization microscope and the optical anisotropy was observed by elevating temperature. Good optical anisotropy was thereby observed above 307°C.
  • Test pieces of this polyester were prepared by using the molding machine of example 1 under such conditions that the cylinder temperature and the mold temperature were 350 and 30°C respectively.
  • the flexural modulus of this test piece measured by the same conditions as those of example 1 was 16.2 GPa.
  • the value of Izod impact strength (mold-notch) was 27 kg ⁇ cm/cm, which is high.
  • Heat distortion temperature measured was 252°C (18.56 kg/cm2), showing excellent heat resistance.
  • melt viscosity of this polymer was 2,800 poises at 350°C under the shear rate of 1,000 sec ⁇ 1, showing very good flow characteristics.
  • the logarithmic viscosity of this polymer was 4.0 dl/g.
  • reaction was carried out under nitrogen atmosphere at 250 to 340°C for 3 hours and the pressure was thereafter reduced to 1.5 mmHg after the temperature was elevated to 360°C.
  • Polycondensation reaction was furthermore carried out by heating for more one hour to obtain a brown polymer.
  • Five batches of the polymerization were furthermore carried out under the same conditions and the polymers recovered were ground, using a grinding machine manufactured by Horai Co., Ltd.
  • Test pieces of this polyester were prepared by using the molding machine of example 1 under such conditions that the cylinder temperature and the mold temperature were 350° and 120°C respectively.
  • the bending modulus of this test piece measured by the same conditions as those of example 1 was 16.8 GPa.
  • the value of Izod impact strength (cut-notch) was 20 kg ⁇ cm/cm, which is high.
  • Heat distortion temperature measured was 265°C (18.56 kg/cm2), which shows excellent heat resistance.
  • melt viscosity of this polymer was 7,100 poises at 353°C under the shear rate of 1,000 sec ⁇ 1, which shows very good flow characteristics.
  • the logarithmic viscosity of this polymer was 4.2 dl/g.
  • reaction was carried out under nitrogen atmosphere at 250° to 350°C for 3 hours and the pressure was thereafter reduced to 0.5 mmHg.
  • Polycondensation reaction was furthermore carried out by heating for 0.3 hour more to obtain a brown polymer.
  • Five batches of the polymerization were furthermore carried out under the same conditions and the polymers recovered were ground using a grinding machine manufactured by Horai Co., Ltd.
  • the liquid crystal starting temperature of this polymer was 301°C.
  • Test pieces were prepared by using the molding machine shown in example 1 under such conditions that the cylinder temperature and the mold temperature were 350° and 30°C respectively.
  • the bending modulus measured by the same conditions as those of example 1 was 11.7 GPa and the value of Izod impact strength (mold-notch) was 17 kg ⁇ cm/cm, which is high.
  • the heat distortion temperature measured was 208°C (18.56 kg/cm2), thus showing excellent heat resistance.
  • the melt viscosity of this polymer was 650 poises at 350°C under the shear rate of 1,000 sec ⁇ 1, thus showing good flow characteristics.
  • the logarithmic viscosity of this polymer was 2.9 dl/g.
  • reaction was carried out under nitrogen atmosphere at 250° to 340°C for 3 hours and the pressure was thereafter reduced to 1.5 mmHg.
  • Polycondensation reaction was furthermore carried out by heating for 1.0 hour more to obtain a brown polymer.
  • Five batches of the polymerization were furthermore carried cut under the same conditions and the polymers recovered were ground using a grinding machine manufactured by Horai Co., Ltd.
  • This polyester showed good optical anisotropy above 268°C.
  • Test pieces of this polymer were prepared by using the molding machine of example 1 under such conditions that the cylinder temperature and the mold temperature were 320° and 120°C respectively.
  • the bending modulus measured by same conditions as those of example 1 was 13 GPa and the value of Izod impact strength (mold-notch) was 15 kg ⁇ cm/cm, which is high.
  • the heat distortion temperature measured was 241°C (18.56 kg/cm2), thus showing excellent heat resistance.
  • the melt viscosity of this polymer measured by using Kota type flow tester manufactured by Shimazu Corporation at 320°C under the shear rate of 1,000 sec ⁇ 1 was 1,800 poises, thus showing good flow characteristics.
  • the dynamic loss peak temperature was measured by means of Rheovibron DDV-II-EA manufactured by Toyo Boldwin Co., Ltd. under such conditions that the frequency, the rate of temperature rise and the distance between chucks were 110 Hz, 2°C/minute and 40 mm respectively and the glass transition temperature was found to be 234°C, which showed that the polymer had high heat resistance.
  • the reaction was carried out under nitrogen atmosphere at 130°C to 250°C for 5 hours and furthermore at 250° to 340°C for 2 hours. After elevating the temperature at 350°C, the pressure was reduced to 0.2 to 0.8 mmHg and the reaction was furthermore carried out for 0.5 to 1 hour more to obtain a brown polymer.
  • Liquid crystal starting temperature, melt viscosity (measured at liquid crystal initiation temperature +40°C under the rate of shear of 1,000 sec ⁇ 1) and logarithmic viscosity were measured.
  • Test pieces of this polymer were prepared by using the molding machine of example 1 under such conditions that the cylinder temperature was liquid crystal initiation temperature +40°C and the molding temperature was 30°C and the bending modulus and heat distortion temperature were measured under the same conditions as those of example 1. These results are shown in Table 6.
  • polyesters of the present invention have good flow characteristics and excellent mechanical properties and heat resistance.
  • polyesters of comparison examples had inferior flow characteristics and heat resistance to those of polyesters of the present invention (Comparison example 8), had poor heat resistance (Comparison examples 9, 12 and 13), or were solidified during polymerization and homogeneous melt polymerization was impossible (Comparison examples 10 and 11).
  • Aromatic polyesters of the invention have melting points below 400°C in many cases and can be melt-moldable by means of ordinary melt moldings such as extrusion molding, injection molding, compression molding, blow molding and the like to prepare fibers, films, three dimensional moldings, containers and hoses. They can be used for electronic parts such as connectors and the like, optical fiber parts such as tension members and the like, chemical apparatus such as packings for packed columns and the like, automotive parts, containers for electronic ranges, IC sealing materials, plastic magnets and so on.
  • melt moldings such as extrusion molding, injection molding, compression molding, blow molding and the like to prepare fibers, films, three dimensional moldings, containers and hoses.
  • They can be used for electronic parts such as connectors and the like, optical fiber parts such as tension members and the like, chemical apparatus such as packings for packed columns and the like, automotive parts, containers for electronic ranges, IC sealing materials, plastic magnets and so on.

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Claims (13)

  1. Aromatischer Polyester, bestehend aus den nachstehend beschriebenen Struktureinheiten (i), (vi), (vii) und (v), mit oder ohne Struktureinheit (viii), worin das Molverhältnis von Struktureinheit (i) zur Gesamtmenge der Struktureinheiten [ (i) + (vi) + (vii) + (viii)
    Figure imgb0069
     ] 60 bis 90%, das Molverhältnis der Struktureinheiten [ (vi) + (vii) + (viii)
    Figure imgb0070
     ] zur Gesamtmenge der Struktureinheiten [ (i) + (vi) + (vii) + (viii)
    Figure imgb0071
     ] 10 bis 40%, das Molverhältnis der Struktureinheit (vi) zur Gesamtmenge der Struktureinheiten [(vi) + (vii)] 50 bis 95%, das Molverhältnis der Struktureinheit (vii) zur Gesamtmenge der Struktureinheiten [(vii) + (viii)] 5 bis 100% und das Molverhältnis der Gesamtmenge der Struktureinheiten [ (vi) + (vii) + (viii)
    Figure imgb0072
     ]
    Figure imgb0073
     zur Struktureinheit (v) 1 beträgt; und dessen logarithmische Viskosität einer Lösung in Pentafluorphenol mit 0,1 g/dl bei 60°C 1,0 - 20 dl/g beträgt
    Figure imgb0074

            (̵OXO)̵   (viii)

    Figure imgb0075
     worin X ausgewählt ist aus
    Figure imgb0076
     und die Carbonylgruppen in der Struktureinheit (v) jeweils in m- oder p-Position zueinander stehen, wobei mehr als 65 Mol-% in p-Position stehen.
  2. Aromatischer Polyester nach Anspruch 1, umfassend die Struktureinheiten (i), (v), (vi) und (vii), worin 65 - 85 Mol-% der Carbonylgruppen der Struktureinheit (v) jeweils in p-Position zueinander stehen.
  3. Aromatischer Polyester nach Anspruch 1 oder 2, umfassend die Struktureinheiten (i), (v), (vi) und (vii), worin das Molverhältnis der Struktureinheit (vi) zur Gesamtmenge der Struktureinheiten [(vi) + (vii)] 60 bis 80% beträgt und 72 - 77,5 Mol-% der Carbonylgruppen der Struktureinheit (v) jeweils in p-Position zueinander stehen.
  4. Aromatischer Polyester nach Anspruch 1, umfassend die Struktureinheiten (i), (v), (vi), (vii) und (viii), worin das Molverhältnis der Struktureinheit (viii) zur Gesamtmenge der Struktureinheiten [(vii) + (viii)] 10 bis 80% beträgt und X in Struktureinheit (viii) ausgewählt ist aus
    Figure imgb0077
  5. Aromatischer Polyester nach Anspruch 4, worin das Molverhältnis der Struktureinheit (i) zur Gesamtmenge der Struktureinheiten [ (i) + (vi) + (vii) + (viii)
    Figure imgb0078
     ] 65 bis 80% beträgt und 100 Mol-% der Carbonylgruppen der Struktureinheit (v) jeweils in p-Position zueinander stehen.
  6. Formteil, hergestellt entweder durch Extrusion oder Spritzguß eines aromatischen Polyesters nach irgendeinem der Ansprüche 1 - 5.
  7. Formteil nach Anspruch 6, worin der aromatische Polyester die Struktureinheiten (i), (v), (vi), (vii) und (viii) umfaßt, das Molverhältnis der Struktureinheit (vi) zur Gesamtmenge der Struktureinheiten [(vi) + (vii)] 60 bis 80% beträgt und 72 - 77,5 Mol-% der Carbonylgruppen der Struktureinheit (v) jeweils in p-Position zueinander stehen.
  8. Formteil nach Anspruch 6, worin der aromatische Polyester die Struktureinheiten (i), (v), (vi), (vii) und (viii) umfaßt, das Molverhältnis der Struktureinheit (i) zur Gesamtmenge der Struktureinheiten [ (i) + (vi) + (vii) + (viii)
    Figure imgb0079
     ]
    Figure imgb0080
     65 bis 80%, das Molverhältnis der Gesamtmenge der Struktureinheiten [ (vi) + (vii) + (viii)
    Figure imgb0081
     ]
    Figure imgb0082
     zur Gesamtmenge der Struktureinheiten [ (i) + (vi) + (vii) + (viii)
    Figure imgb0083
     ] 35 bis 20%, das Molverhältnis der Struktureinheit (viii) zur Gesamtmenge der Struktureinheiten [(vii) + (viii)] 10 bis 80% beträgt, in Struktureinheit X ausgewählt ist aus
    Figure imgb0084
     und 100 Mol-% der Carbonylgruppen der Struktureinheit (v) jeweils in p-Position zueinander stehen.
  9. Verfahren zur Herstellung eines aromatischen Polyesters nach Anspruch 1, umfassend die folgenden wiederkehrenden Einheiten
    Figure imgb0085
     (worin X ausgewählt ist aus
    Figure imgb0086
     worin das Verfahren die Reaktion der folgenden Verbindungen umfaßt:
    (a) p-Hydroxybenzoesäure
    (b) 4,4'-Dihydroxybiphenyl
    (c) Hydrochinon
    (d) Terephthalsäure oder ein Gemisch aus Terephthalsäure und Isophthalsäure, das mehr als 65% Terephthalsäure enthält,
    mit oder ohne
    (e) einer Dioxyverbindung, ausgewählt aus t-Butylhydrochinon, Phenylhydrochinon, 2,6-Dihydroxynaphthalin, Chlorhydrochinon und Methylhydrochinon,
    wobei die Molanteile der Verbindungen (a) bis (e) zueinander, unter der theoretischen Annahme, daß die gesamte verfügbare Terephthalsäure-Verbindung (d), gegebenenfalls zusammen mit einer Isophthalsäure-Verbindung (d), mit jeder der Verbindungen (b), (c) und gegebenenfalls (e) reagiert, so gewählt werden, daß die wiederkehrenden Einheiten in den folgenden prozentuellen Molanteilen vorliegen: (1) (i) / [(i) + (ii) + (iii) + (iv)] x 100 Mol-% = 60 - 90; (2) [(ii) + (iii) + (iv)] / [(i) + (ii) + (iii) + (iv)] x 100 Mol-% = 40 - 10; (3) (ii) / [(ii) + (iii)] x 100 Mol-% = 50 - 95; und (4) (iii) / [(iii) + (iv)] x 100 Mol-% = 5 - 100.
    Figure imgb0087
  10. Verfahren nach Anspruch 9, worin der aromatische Polyester die Struktureinheiten (i) bis (iii) umfaßt, worin 65 - 85 Mol-% der Carbonylgruppen der Struktureinheiten (ii) und (iii) jeweils in p-Position zueinander stehen.
  11. Verfahren nach Anspruch 9 oder 10, worin der aromatische Polyester die Struktureinheiten (i) bis (iii) umfaßt, das Molverhältnis der Struktureinheit (ii) zur Gesamtmenge der Struktureinheiten [(ii) + (iii)] 60 bis 80% beträgt und 72 - 77,5 Mol-% der Carbonylgruppen der Struktureinheiten (ii) und (iii) jeweils in p-Position zueinander stehen.
  12. Verfahren nach Anspruch 9, worin der aromatische Polyester die Struktureinheiten (i) bis (iii) umfaßt, das Molverhältnis der Struktureinheit (iv) zur Gesamtmenge der Struktureinheiten [(iii) + (iv)] 10 bis 80% beträgt und X in der Struktureinheit (iv) ausgewählt wird aus
    Figure imgb0088
  13. Verfahren nach Anspruch 12, worin im aromatischen Polyester das Molverhältnis der Struktureinheit (i) zur Gesamtmenge der Struktureinheiten [ (i) + (ii) + (iii) + (iv)
    Figure imgb0089
     ] 65 bis 80% beträgt und 100 Mol-% der Carbonylgruppen der Struktureinheiten (ii) bis (iv) jeweils in p-Position zueinander stehen.
EP87904936A 1986-07-28 1987-07-23 Aromatische polyester mit guter wärmebeständigkeit Expired - Lifetime EP0275324B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP61175742A JP2525370B2 (ja) 1986-07-28 1986-07-28 流動性の改良された芳香族ポリエステル
JP175742/86 1986-07-28
JP61183374A JPH0798859B2 (ja) 1986-08-06 1986-08-06 全芳香族ポリエステル射出成形品
JP183374/86 1986-08-06
PCT/JP1987/000536 WO1988000955A1 (en) 1986-07-28 1987-07-23 Aromatic polyesters with good heat resistance

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EP0275324A1 EP0275324A1 (de) 1988-07-27
EP0275324A4 EP0275324A4 (de) 1990-03-21
EP0275324B1 true EP0275324B1 (de) 1995-12-27

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DE (1) DE3751653T2 (de)
WO (1) WO1988000955A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3629211A1 (de) * 1986-08-28 1988-03-03 Basf Ag Vollaromatische thermotrope polyester
DE68928258T2 (de) * 1988-10-11 1998-03-26 Amoco Corp Hochfeste polymer gemische aus hydrochinon polyterephthalaten, enthaltend reste aus p-hydroxybenzoesäure
JPH02276819A (ja) * 1988-12-29 1990-11-13 Kawasaki Steel Corp 芳香族ポリエステルおよび芳香族ポリエステルアミドならびにそれらを用いた繊維、樹脂組成物
WO2005123804A1 (ja) 2004-06-22 2005-12-29 Toray Industries, Inc. 液晶性樹脂、その製造方法、液晶性樹脂組成物および成形品

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EP0275324A1 (de) 1988-07-27
DE3751653T2 (de) 1996-07-18
EP0275324A4 (de) 1990-03-21
DE3751653D1 (de) 1996-02-08
WO1988000955A1 (en) 1988-02-11

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